Oxadiazole compounds



United States Pate t 21? 1 911 oxidized to .the triazole ring and in this way aconipound 2,845,419 produced of the ,formula V OXADIAZOLE COMPOUNDS 3 N--.N-Ri

Adolf Emil Siegrist, Basel, and Franz Ackermann, Biu- 5 ningen, Switzerland, assignors to Ciba Limited, Basel, Switzerland, a Swiss firm No Drawi ,A l'c o. .Febru 6 1956 l Ser-iiil 1 1:. 533,445 ary in which A "indicates "an .arylradical frveekfro m fhy'droxyl 10 groups and condensed with the triazole ring lnthernan- Clams applicsaflfigsswnzefland ner indicated by the valence bonds, and R is an aryl e wary radical whichzcontains'in pepositionto ithe-bond-b y which 10 Claims. (Cl. 260-240) it isettached to t a ole ri g, a cariboxy ac dt Q P which may if desired be functionally. converted,- from This invention relates to .new, fluorescent, practically such a compound, by condensation with hydrazinefland uncolored oxadiazole compounds which, as illustrated by by treatmentwith agentsjwhich split out Water, the the compound of the formula: desired oxadiazole compounds areobtained.

are free from .hydroxyl groups ,and contain at least one As p-aminoaryl carboxylic acids there are advantaarylzresidue whidhzisz attachedonone sidegto'an oxadiazole 'geous'ly used -p-aminobeuzoic acids, for example p-amino- -ring :andjin p -position :thereto :to ;a l-:.2:3etriazole ring, benzoic acid which is not further substituted. As afzio the two carbon atoms of which are at the .same time components there can be used aminoaryl compounds of ring members of arfurther i'aryl .aradical. the benzene series such as 1,:3-diaminobenzene, lfamino- The new compounds contain :thus .at least :once the 3-methoxyl-methyl-benzene, l-amino-3z4 dimethoxy atom grouping benzene or preferably of the naphthalene series, which couple in adjacent position to the amino group, e. g. 2-

(2) o e 40 amino-naphthalene being suitable and the amino-naphthar g lene sufonic acids being especially suitable which con- 1 la tain from 1-3, preferably .two sulfonic acid groups. 2-

m amino-napthalenes which "couple in l-position or 1- aminonaphthalenes which couple in 2-position are concerned. As examples may be mentioned:

' I r 7 w I l-aminonap'hthalene-4- or -*5-sulfonic acid,

i ivhlch W radical m 1.116 Laminonaphthalene-i, -6- or -7- sulfonic acid, indicated by .the valence bonds with .the trlazole r ng 2 aminonaphtha1ene 3.:5;di su1fonicacid, I and R lndlcates an aryl radical attached in p-positlon 2 aminonaphtha1ene 5fl ai sulfonic acid,

to the two hetero rings. 1-aminonaphtha'lene-3:S-di-sulfonic acid,

"These m p s dbtained when aryl 1-aminonaphthalene-4:8-di-sulfonic acid. carboxylic acid, which contains in p-position .to the v carboxyl group a dlazotlsablesammogmllp or t The intermediate products of the formula 3 can now,

containinesubstituent c ver e into h a pr in the form of the free acids or as their functional su l 0n the on 'h 1 n s y after conversion derivatives, especially as acid halides, be condensed with of th S id u l lk i t a P y amino l' up, hydrazines. In the first mentioned case sulfur trioxide diaZO iZ 0f the amino p Y 9 P is suitable as condensing agent, 'especiallywhen dissolved .of the diazocomp undfon with anammoaryltcomin anhydrous sulfuric acid (oleum), since it not only Pound freeffom y l gfollpsflnd l t coupling \eflects the condensation to the carboxylic acid hydrazide inflle adlacellt P sition-t0 the l pyz x but also the desired ring closure to the oxadiazole in tion theo-aminoazo p n iihereby p d one Working operation. Sulfona'ting ageuts generally the triazole ring rand, on the other =hand, to condensation can advantageously be used, that is to say in addition to with a hydrazine on the carboxyl roup followed by the oleum already mentioned also, for example, chloroxadiazole ring closure by means of an agent -'which sulfonicacid. When, as in the case ofthe acid halides, splits out water. It is clear that the individual reactions no special condensing agent is necessary, another 'Waterrequired for the production of the new compounds can splitting agent can be used for the ring-closure, such as be carried out in varying :sequences. a r I thionyl chloride, aluminum trichloride or phosgene.- This Thus for :example, a p-aminoaryl:carboxylic;acid acan modification of :the process is indicated in those cases in be ,diazotized, tthe diazo compound coupled with .an which the sulfonating agent would in addition to the aminoaryl compound which coup1es,in;,the adjacentposicondensation and the ring closure also effect an undetion to" ;the. amino group, :the .OrBmiHOHZO -cgrouping siredsulfonation. It should, however, 'beremarked that even with oleum such a sulfonation does not take place easily either in the radicals R or in the radicals A, so long as the radicals A already contain one or even two sulfonic acid groups.

According to the constitution of the hydrazines a variety of end products can be obtained according to the present process. Thus, for example, unsubstituted hydrazine (H N--NH advantageously in the form of hydrazine sulfate can be condensed on both sides with carboxylic acids of the specified constitution and the ring closure carried out. In a similar manner dicarboxylic acid dihydrazides, for example the dihydrazide of oxalic acid (H N-NHOO-COHN-NH or of terephthalic acid can be condensed on both sides with the mentioned carboxylic acids and in these cases a double ring closure carried out. Finally dicarboxylic acid dihydrazides which are aroylated on one side, or preferably monoaroyl hydrazines such as benzoylhydrazine can be reacted on one side a carboxylic acid of the specified constitution and again ring closure carried out. By these methods oxadizole compounds are obtained of the formula: i v.

in which A indicates an aryl radical condensed with the triazole ring in the manner indicated by the valence bonds, R is an aryl radical attached in p-position to the hetero rings, R is any suitable radical, preferably a benzene radical attached in p-position to the oxadiazole rings, R is an aryl radical or likewise a radical of the consitution (5) -Rr-NN and m and it each indicates a whole number which is at the most 2.

According to another modification of the present process the procedure is as follows:

A p-aminoaryl carboxylic acid or an aryl carboxylic acid which contains in p-position to the carboxylic acid group a substituent convertible into an amino group, if desired in the form of the acid halide, is condensed with a hydrazine and ring closure to the oxadiazole is then carried out. After the mentioned substituent, if present, has been converted into the amino group (for example a nitro group reduced), the amino compound is diazotizcd and the diazo compound coupled with an amino-aryl compound which couples in adjacent position to the amino group.

Finally, in the resulting compound, which contains an azo group attached on both sides to aryl nuclei which are free from hydroxyl groups and of which one contains an amino group in adjacent position to the azo group and the other is attached in p-position to the azo group to an oxadiazole ring, the amino azo grouping is oxidized to the triazole ring.

What has been said in connection with the first mentioned modification, especially as regards the selection of the starting materials, likewise applies here in a corresponding manner. Accordingly, for the oxidation to .the

4 -triazoles advantageously compounds of the following formulae are used:

The oxidation to the triazoles can becarried out in the manner known per se, for example with copper compounds and advantageously with copper tetrammines. Likewise all the other reactions necessary for the production of the final products of the process and also of the starting materials thereof, can be carried out by known per se.

The new oxadiazole compounds of the constitution set forth above are suitable for the improvement as regards optical properties, as a rule for the optical brightening, of a variety of materials, especially organic materials and primarily textile materials, with the production of valuable results.

The application of the fluorescent compounds which are used for brightening purposes can take place in such a manner that the material to be improved is saturated with a solution, especially an aqueous solution, or a dispersion of the compound concerned and after hydroextracting or squeezing out, .dried. In addition to the mentioned aqueous solutions, solutions in organic solvents can also be used for the improving process of this invention. It is also possible to treat materials with the compounds in dispersed form, for example with dispersions which are obtained with dispersing agents such as soaps, soap-like substances, polyglycol ethers of fatty alcohols, sulfite waste liquor or condensation products with formaldehyde of naphthalene sulfonie acids which may be alkylated.

The compounds suitable as brightening agents can also be brought into use in the course of the process of manufacture of the materials to be improved, for example by including them in a paper pulp or a viscose solution which is to be used for the production of films or threads, or in other spinning masses, for example containing a linear synthetic polyamide or a spinning solution of acetyl cellulose.

The compounds to be used as brightening agents can also be applied as follows:

(a) In admixture with dyestutfs or as addition to dye baths or printing, discharge or reserve pastes. Further also for the after-treatment of dyeings, prints or discharge prints.

(b) In admixture with chemical bleaching agents or as additions to bleaching baths.

(0) In admixture with finishing agents such as starch or synthetic finishes. The compounds to be used according to the invention can for example also be added to the baths used for the production of a crease-proof finish.

(d) In combination with washing agents: The washing agents and brightening agentscan be separately added methods to the washing baths to be used. It is also advantageous to use washing agents which contain brightening agents admixed therewith. As washing agents are suitable for example, soaps, salts of sulfonate washing agents, as for example, of sulfonated benzimidazoles substituted on the 'Z-carbon atom by'higheralkyl radicals, also salts of monocarboxylic acid esters of 4-sulfophthalic acid with higher fatty alcohols or salts of fatty alcohol sulfonates, alkylaryl sulfonic acids or condensation products of higher fatty acids with aliphatic hydroxy or 'amino-sulfonic acids. Non-ionic washing agents can also be used, for example polyglycol ethers which are derived from ethylene oxide and higher fatty alcohols, alkyl phenols ;or fatty amines.

The washing agents of the above specified type can also contain the customary washing agent additions, such as alkali metal carbonates, phosphates, pyrophosphates, poly-phosphates, metaphosphates, silicates, perborates or percarbonates, so long as the brightening agents are compatible with such additions. It ;is also possible to prepare washing agents which consist solely or for the most part of inorganic compounds with cleansing effect and the brightening agents. The production of the mixtures of the washing agents and optical brightening agents takes place in a simple manner by mixing and/or grinding of the components together. In this case it may be of ad-. vantage to use one or the other component in the dissolved or molten condition for the purpose of facilitating distribution.

In general a small addition of the optical improving agents to the washing agents sufiices. There are concerned, for example, quantities of 0.1 to 5 percent calculated on the washing agent. 'Also smaller quantities, for example, 0.01 percent or even less can be added. Also mixtures with other known brightening agents can be :used. The washing agents are used by the customary washing processes. In this manner materials to be cleansed can be simultaneously washed and brightened.

v As materials of which the optical properties can be improved, the following maybe mentioned:

(A) Textile materials quite .generally which can exist in any form, for example, as fibres, threads, yarns, woven or knitted goods or in the form of felt and all goods manufactured therefrom; such textile materials can consist of: natural materials of animal origin, such as wool and silk, but primarily cellulosic materials, such as cotton, hemp, flax, linen, jute and ramie, also semi-synthetic materials, such as regenerated cellulose, for example, artificial silk, viscose, including staple fibre, further of cellulose esters, such as cellulose butyrate and especially acetyl cellulose, furthermore of synthetic materials or more NaOsS those which are obtainable by polycondensation, for example polyamides such as nylon or Perlon." The brightening eifect obtained. on these materials has a good fastness to chlorine.

(B) Fibrous materials of other types which are not textile materials and which can be of animal origin,

(C) Plastic materials generally which can be present in any form, forexample :as powder, film, lacquer, resin or moulded objects, also natural or synthetic colloids, such as gelatine or starch, natural or synthetic rubber, synthetically produced ,glasses .or also photographic emulsions and also .filmsor papers produced .from .the latter, other substances .of natural .or artificial, organic origin, such as.oils,,fats or carbohydratesintended.as food-stuffs, for example .flour, .sugar etc., or finally cosmetic prepara- .tions.

When the new .oxadiazolecompoundsare usediin combination'with other improving agents, for example by any of .themethods .set forth .under .(,a:) to (d) above, this combined treatment is advantageously carried out with the aid of suitable preparations. The e stable preparations contain compounds of the constitution set forth above, for example such of the Formula 4, and also further textile treating agents, for example dyestuffs, chemical bleaching agents, ,Ifinishing agents, or especially washing agents.

The following examples illustrate the invention, the parts being by weight unless otherwise stated and the relation between part .by weight and part by volume being the same as that between the-kilogram and the litre.

Example 1 I Into .a solution of 6.5 parts of hydrazine sulfate .in 1190 parts of oleum (27% S03), with stirring and cooling,

52 .parts of the trisodium salt of 4-[5:7-disulfonaphthol:2:4:5-triazol-(2)J-benzoic acid of the formula tration from asmall quantity of impurities and the filtrate such as feathers, hair, hides and skins and leather obtained is salted out with sodium chloride. After cooling, filtration with suction and drying of the residue, the condensation product of the formula:

O cOm-m -4 l/ S OaNa is obtained as a weak yellow colored powder which is soluble in water. When exposed to ultra-violetrays, the aqueous solution has a bluish fluorescence.

By using instead of the above mentioned 4-f5z'7 -disulfonaphtho-lz2'z4:5-triazolyl-(2)l-benzoic acid equimolecula-r quantities of 4-[3:6-disulfonaphtho--l"':2':4z-5- triazolyl- (2) ]-benzoic acid, -4- EST-,suIfQna htho-I' 2: 4: 5- triazolyl- (2)]-benz0ic acid or 4-[.6'-sulfonaphtho-1':2':- 4:5-triazolyl-(2) ]-benzoic acid products are obtained with similar properties.

The 4-[527' disulfonaphtho-l'zZ':4z5-triazolyl-(2) benzoic acid used as starting material can be obtained by diazotization of p-aminobenzoic acid, coupling with 2- 7 8 aminonaphthalene-S:7-disulfonic acid and boiling the temperature is then brought within 30 minutes to 65' C. resulting dyestuff with ammoniacal copper sulfate soluand stirring then carried out for 12 hours at 65-70 C. tion. The whole is allowed to cool, the brown reaction solution Example 2. is poured into ice water and neutralized with 30% sodium hydroxide solution with cooling so that the temperature does not exceed 30 C. Then heating is carried out to diazole in 250 parts of ice water and 50 parts by volume a of concentrated hydrochloric acid, are tetrazotized at 02 7040 n the condensauon Product of'thc SOzNa C. with 50 parts by volume of 4 N-sodium nitrite solu- Y tion. After 1 hour, the tetrazo solution is stirred for 10 O O minutes with a little blood charcoal and filtered from a ll ll small quantity of impurities. The 'tetrazo solution is added dropwise within minutes to a neutral solution 25.2 parts of 2:5-bis-[4"-aminophenyl-(1)]-1:3:4-oxaof 60.6 parts of 2-amino-naphthalene-S:7-disulfonic acid Naoas in 250 parts of water at 03 C. Thereupon by dropwise addition of sodium acetate solution, the acid reaction to Congo red is caused to disappear and further stirring is Naoas continued for 16 hours at 20 C. When the coupling is complete, the'resulting dyestufi is completely separated Separated with Sodium chloride- Aficl 60011118, filtrawith sodium chloride, filtered off and the filter residue no tion with s c ion and drying of the filter residue, a bright purified by dedissolving in water, salting out and'drying powder is obtained of which the aqueous solution, when the filter residue. The scarlet red dyestuff of the formula exposed to ultra-violet rays, has a bluish fluorescence.

Og Q -O NAOaS NH:

BOzNa N; OrNa is dissolved in 1,000 parts of hot water and oxidized to When there are used instead of the above described the ditriazole compound by boiling for 7 hours with 120 4-[5'z7-disuliFonaphtho-1:2z4z5-triazolyl-(2)] benzoic P3115 0f (ifystauille 1 1 sulfate in the pres'ence of acid equimolecular quantities of 4-[3:6'-disulfonaphthoparts by volume of ammomum hyfiroxlde q 1':2:4:5-triazolyl-(2)]-benzoic acid, 4[5'-Sulfonapl1tho After coohng, the dlmazole compound separated wlth 1:2:4:5-triazolyl-(2)J-benzoic acid 4[6-sulfonaphthr sodium chloride, filtered and the filter residue, for further 1,:2,:4:5 tl iaZo1y1 (2) benzoic acid or 4 [7l sulfonaph i F de'coppered m 2000 Parts of hot water by 40 tho-l'z2z4z5-triazolyl-(2)l-benzoic acid products are addition of 100 parts by volume of 30%.sod1um hybt d h i1 ti droxide solution at 80-85 C. The whole is filtered hot 0 mm Proper Products with similar properties are hkewise obtained and the ditriazole compound separated from the filtrate by addition of sodium chloride. Stirring is carried out in when lPstead 9 the above menilfmed benzoic acld monothe cold followed by filtration and drying of the filter hydrallde equlmoleclllal' quantliles am used of P- residue. The ditriazole compound of the formula benzoic i monohydrazide. py ic id NaOiS 1 SOzNa Naois I o OsNa forms a bright, weak yellow colored powder, the aqueous monohydrozide, o-methoxybenzoic acid monohydrazide solution of which, when exposed to ultra-violet rays has or cinnamic acid monohydrazide. a bluish fluorescence.

By using instead of the above mentioned Z-amino- Example 4 naphthalene 5:7-disulfonic acid equimolecular quantities of 2-amino-naphthalene-3:6-disulfonic acid, Z-aminonaphthalene 5 sulfonic acid, 2-aminonaphthalene-6- sulfonic acid or Z-aminonaphthalene-7-sulfonic acid, products with similar properties are obtained.

The above mentioned 2:5-bis-[4'-aminophenyl-(1')]- 1:3:4-oxadiazole can be prepared according to French Patent No. 1,080,106, Example 8, paragraph 3 et seq.

Into 190 parts of oleum (27% S0 with stirring and cooling, 9.7 parts of terephthalic acid dihydrazide and 52 parts of the trisodium salt of 4-[5:7-disulfonaphtho I:2'2425-triaz0lyl-(2)J-benzoic acid are introduced slowly so that the temperature does not exceed 30 C. The temperature is then brought within 30 minutes to 65 C. and stirring then continued for 12 hours at 65 C. The whole is allowed to cool and the light brown Example 3 70 reaction solution poured into ice water and neutralized Into 190 parts of oleum (27% S0 are slowly introwith 3% sodium hydroxide solution with cooling so that dnced with stirring and cooling so that the temperature the temperature does not exceed 30 C. Heating is then does not exceed 30 C., 13.6 parts of benzoic acid monocarlied Ou to followed y fi on from hydrazide and- 52 parts of the trisodium salt of 4-[5':7'- small quantities of impurities and the filtrate is precipidisulfonaphtho-l:2';4;5-triazolyl-(2)] 'benzoid acid. The tated with sodium chloride. After cooling, filtration with suction and drying of the filterresidue, "the condensation productof the' for-rnula I NaOIS N803 is :ob'tai-ne'd as a bright-powder of wlrtic'h-the aqueous solution when exposed to ultra-violet *rays, has a bluish fluorescence.

By using instead of the above mentioned terephthalic acid dih-ydra-zide 5.9 parts of oxalic acid dihydrozide, the condensation product of the formula:

l mit- T? NKT'OEQEEQEGV is obtained as abrig'ht, weak yellowish powder of similar properties.

Products with similar properties are likewise :obtained .when {insteadiof the above mentioned 4 -.[5 f:7"\-disu1fonaphtho-l':2:4:5-triazolyl-(2)l-benzoic acid an .equimolecular quantity of 4-[3:6-disulfonaphtho-1:2:4:5- triazolyl-(Z) l-benzoic acid is used.

Example 5 p 24.7 parts of 2-[4'1chlorophenyl-(l);l-5-[4"-aminoparts of ice water and 30 parts by volume of hydrochloric acid of 30% strength with 25 parts by volume of 4N- sodium nitrite solution at 0-2 C. A solution of 14.3 iparts of 52-:aminonaphthalene in .75 parts .by volume of glacial acetic acid are added to :this diazo compound in the course of 60 minutes at50 2 C. When the coupling is :complete, the violet re'd xdyestufi 50f the formula:

is obtained as aifaintly reddish colored powder, of which the solution in trichlorobenzenmwhen exposed to'ultraviolet rays, has :a bluish fluorescence.

zole an equimolecular =quantity'of 2-[ 4'-methoxyphenyll ")1-5-fE-4-aminophenyl-(1"")] 1:3 :4- oxadiazole, 2- IZ4'-methylphenyl-(l) ]-5-'[4"-aminophenyl-f('l"-)-] 1:3 :'4- oxadiazole or Z-phenyl-S-[4" aminophenyl-( 1")l l :3 :4- oxadiazole, products with similar properties are likewise obtained.

OaNa

Products with-similar properties .arealso :obtainedwhen instead of the above mentioned .2-amino-naphthalene an equimolecular quantity of 1-amino-3-methoxy-4-methylbenzene ,or l=amino-3.: 4tdimethoxy benzene ;is .used.

The .2-;[4'- chl0r0phenyl-(1')J .5 ;[4--aminqphen yl- (1")]-1:3:4-oxadiazole mentioned above can be prepared as follows:

Into 192 parts of oleum (27% free S0 are slowly introduced'with cooling and stirring so that the temperature does not exceed 30 C., 51.2 parts of p-chlorobenzoic acid monohydrazide and 50.1 parts of p-nitrobenzoic acid. The temperature is then brought Within 30 minutes to 65 C. and stirring continued for 5 to 6 hours at 75 to C. The whole is allowed to cool, the reaction mixture is poured into 1000 parts of ice water with stirring, the condensation product separating in the iorm of a white suspension. The mixture is filtered with suction, washed with cold and then with warm water until the reaction is neutral to Congo, and finally the filterresidue is stirred in 1000 parts of water at 70 to 80 C;, the mixture being rendered distinctly alkaline with'sodium carbonate. After filtering with suction, washing with water and drying, there is obtained in good yield 2-l4'- chlorophenyl (1')] 5 [4-nitrophenyl-(1"')]-1':3 :4- oxadiazole in the form of -a white powder which, after recrystallization gfrom .chlorobenzene, melts at '254- 259 .C. Y

. 42 partsof.2-i[ 4' ch1oropheny1-v(1')J-5e[ 4"enitrophenyl- (51 i|.-1:1-3::4-.oxadiazole .are reduced ibyb ein-gsb oiled un'cler 'i'e'fluxtforflfl hours with=stirring in 1500 parts by volumesof ethanol and by adding 50 parts of concentrated hydrochloric acid and parts of-iron powder. The reaction mixtur is rendered alkaline witha solution of-sodium hydroxide of 30% strength, filtered :hot and the filtrate dilutedwith the same volume of Water, the 2-'[4-,ch1oro- -phenyle( 1'.) ]-;5-[4" -aminophenyl-(1)ll :3 :4-oxadiazole separates oifdn the :form of a white :substance. After filtering with suction, washing with water and recrystalliza- -tion from aqueous ethanol the product melts at 201- Example 6 25.2 parts of 2:5-bis-[4-aminophenyl-(vl')Zl-1:3.:4- .oxadiazole are tetrazotized as described in Example 2. Tothis ten'azo solution there is-added in thecourse of one .hour asolutioniof .21.6 p arts of 1:3 diaminobenzeneain 2,845,419 11 12 100 parts by volume of methyl alcohol at -2" C. When has been washed with the said sodium salt of Z-heptathe coupling is complete, the red dyestufl of the formula decyl-N-benzyl-benzimidazyl-disulfonic acid alone.

HzN H:

is filtered off, washed with water, freed from impurities Example 11 by boiling with alcohol and dried.

25.7 parts of the dyestuff obtained are boiled under To a paper pulp, containing 100 parts of bleached sulreflux for 12 hours with stirring in 350 parts by volume fite cellulose, in a hollander there are first added 2 parts of pyridine with 40 parts of copper acetate. After coolof rosin-size and after 15 minutes 0.5 part of the coming, the reaction mass is poured into an excess of aqueous pound obtainable according to Example 1. After a furacetic acid, the residue filtered and washed neutral with ther 15 minutes 3 parts of aluminium sulfate are added. water. For further purification the product is boiled with The paper pulp thus treated is passed through a mixer alcohol and then dried. The ditriazole compound of n to the paper machine.

the formula Paper made in this manner has a higher white content isa red powder, the solution of which in trichlorobenzene, M than a paper made without .the addition of the specified when exposed to ultraviolet rays, has a bluish fluorescence. compound in Example 1.

By melting with an excess of butane sultone at 160-170 i We claim: p C. a water-soluble compound can be prepared. 1. Afluorescent, practically uncolored compound which By using instead of the above mentioned m-phenyleneis free from hydroxyl groups and correspondsto the fordiamine an equimolecular quantity of 1-amino-3-methmula N N I A1 N-RtC C ('3 --B0 A: N I! -L-! LL oxy-4-methyl benzene or l-amino-3z4-dimethoxy-benzene, in which R, and R each represents an aromatic radical products with similar properties are obtained. containing a single ring which is a carbocyclic six-mem- Exam 1 7 bered ring and which is attached in para-position to the heterocychc rmgs, R represents an aromatic radicalcon- Undyed cotton yarn is treated in a bath ratio of 1:30 i i a i l i hi h i a b li ix-mem- 30 minutes at in a bath which coma-111$ P bered ring, and A and A, each represents an aromatic litre gram of the Compound P p according to 50 radical containing, as the sole ringmembers, 4n+2 aro- Examplc After rinsing and y the y ,thus matic nuclear carbon atoms and condensed in the mantreated has a higher white content than the corresponding ner indicated by the valence bonds with the triazole ring, lmlIeatcd materialk, m and 11 each representing a whole number of at the Example 8 most two.

To a sodium hypochlorite bath, containing 2 grams or A c n Practically. unwlorcd compound active chlorine per litre, is added 0.1-0.5 gram per litre which is free from hydroxyl groups and correspondsto of the compound obtained according to Example 2. Celthe formula lulosic material treated in this bath appears whiter than material treated without the addition of the specified compound. N N

Example 9 Undyed textile material of synthetic polyamide fibres, A fi' A for example nylon or Perlon, is treated at a bath ratio 1i \N 1:40 for 1 hour at 85 C. in a bath which contains per litre 0.4 gram of formic acid and 0.2 gram of the compound described in Example 3. After rinsing and drying, t the textile material thus treated has a whiter appearance n which R repres n an a om adical C n g it than a corresponding material treated without this comsingle ring which is a carbocyclic six-membered ring and pound. 1 which'is attached in para-position to the heterocyclic Example 10 rings, and A represents an aromatic radical containing as the sole ring members 4n+2 aromatic nuclear car- The sodium salt of Z-heptadecyl-N-benzyl-benzimidazyldisulfonic acid is mixed with 0.1-0.5 of the comhon atoms and cohqhnsed the f lhdlcfited Y pound described in Example 4. Undyed cotton which the valehce Wlth the mamhl 8 p l has been washed in the customary manner with the resulta Whole number of at the most -v ing mixture has a brighter appearance than cotton which 3. A fluorescent, practicallyuncolored compound which 2,-84'f531tf9 13 H is free from hydroxyl groups and corresponds to the -8. fluorescent, practical ty uncolored: compound formula which hits free' acid statecums :ends to tht: formula N/ & %E 10 9. A fluorescent, practically uncolored compound In Whlch e and s each represents an ammatlc Yadlcal which in its free acid state corresponds to the formula containing a single ring which is a carh'oeyclic-six mein- 0 bered ring, R being attached in para-position to the heterocyclic rings, and A represents a naphthalene -radii 1 cal condensed in the manner")inrlicetted hy the valence I a bonds with the triazole ring. I I 7 g V l v 4. A fluorescent, practically uncolored compound; i which is free from hydroxyl grpupsand in itsifreeacid I state corresponds to the formula 7 iv Hols soar).

in which n represents a whole number of at the most 2.

5. A fluorescent, practically uncolored compound which is free from hydroxyl groups and in its free acid state corresponds to the formula in which R represents a monocyclic benzene radical and m and n each represents a whole number of at the most 2.

6. A fluorescent, practically uncolored compound which in its free acid state corresponds to the formula 7. A fluorescent, practically uncolored compound which in its free acid state corresponds to the formula H018 SOsH H0: 50:

-10.; A fluorescent, practically uncolorcd compound which, in, its ircc acid stat: corresponds to 1h? formula Refer e nces Cited in the of this fiatent UNITED STATES PATENTS V Brunner et a1. Jan. 12,1954 2,668,777 Gold et a1 ..Feb. 9, 1954 2,726346 Tr skqn Dad. 6, 1955 2,765,394 Sicgrist et a1. Oct. 2, 1956 .OTHER R N E Q LandoltfAmQ Dyestuff RepdrtcL'APril 18, 1949, page" f Scr. Nd LfWEndt, (A. P. 0. 

1. A FLUORESCENT, PRACTICALLY UNCOLORED COMPOUND WHICH IS FREE FROM HYDROXYL GROUPS AND CORRESPONS TO THE FORMULA
 10. A FLUORESCENT, PRACTICALLY UNCOLORED COMPOUND WHICH IS ITS FREE ACID STATE CORRESPONDS TO THE FORMULA 